Articles of manufacture including macromolecular block copolymers

ABSTRACT

An article of manufacture includes a macromolecular block copolymer. The macromolecular block copolymer includes a first extruded high molecular weight polymer and a second extruded high molecular weight polymer bonded to the first extruded high molecular weight polymer. The first extruded high molecular weight polymer has a first characteristic rigidity value along a first length, and the second extruded high molecular weight polymer has a second characteristic rigidity value along a second length that is different from the first characteristic rigidity value.

I. FIELD OF THE DISCLOSURE

The present disclosure relates generally to articles of manufactureincluding macromolecular block copolymers.

II. BACKGROUND

In the manufacturing of polymers, it may be desirable to have differentmaterial properties in different regions of an article (e.g., along alength of a linear article).

III. SUMMARY OF THE DISCLOSURE

According to an embodiment, an article of manufacture including amacromolecular block copolymer is disclosed. The macromolecular blockcopolymer includes a first extruded high molecular weight polymer and asecond extruded high molecular weight polymer bonded to the firstextruded high molecular weight polymer. The first extruded highmolecular weight polymer has a first characteristic rigidity value alonga first length, and the second extruded high molecular weight polymerhas a second characteristic rigidity value along a second length that isdifferent from the first characteristic rigidity value.

According to another embodiment, a multi-layered linear article includesa polymeric matrix material layer and a reinforcement layer bonded tothe polymeric matrix material layer. The reinforcement layer includes amacromolecular block copolymer that includes a first extruded highmolecular weight polymer, a second extruded high molecular weightpolymer bonded to the first extruded high molecular weight polymer, anda third extruded high molecular weight polymer bonded to the secondextruded high molecular weight polymer. The first extruded highmolecular weight polymer has a first characteristic rigidity value alonga first length, and the second extruded high molecular weight polymerhas a second characteristic rigidity value along a second length that isless than the first characteristic rigidity value. The third extrudedhigh molecular weight polymer has a third characteristic rigidity valuealong a third length that is different from the second characteristicrigidity value.

According to another embodiment, a reinforced hose includes a polymericmatrix material layer and a reinforcement layer bonded to the polymericmatrix material layer. The reinforcement layer includes a macromolecularblock copolymer that includes a first extruded high molecular weightpolymer, a second extruded high molecular weight polymer bonded to thefirst extruded high molecular weight polymer, and a third extruded highmolecular weight polymer bonded to the second extruded high molecularweight polymer. The first extruded high molecular weight polymer has afirst characteristic rigidity value along a first length, and the secondextruded high molecular weight polymer has a second characteristicrigidity value along a second length that is less than the firstcharacteristic rigidity value. The third extruded high molecular weightpolymer has the first characteristic rigidity value along a thirdlength.

Features and other benefits that characterize embodiments are set forthin the claims annexed hereto and forming a further part hereof. However,for a better understanding of the embodiments, and of the advantages andobjectives attained through their use, reference should be made to theDrawings and to the accompanying descriptive matter.

IV. BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chemical reaction diagram depicting a process of forming amacromolecular block copolymer, according to one embodiment;

FIG. 2 is a diagram of an example of an extrusion setup to generate amacromolecular block copolymer, according to one embodiment;

FIG. 3A is a diagram of an example of a first stage of an extrusionprocess to generate a macromolecular block copolymer where a firstpolymer is extruded through a first extruder, according to oneembodiment;

FIG. 3B is a diagram of an example of a second stage of the extrusionprocess where a second polymer is starting to extrude through a secondextruder while the first polymer is extruded through the first extruder,according to one embodiment;

FIG. 3C is a diagram of an example of a third stage of the extrusionprocess where the first polymer is no longer extruded through the firstextruder, and the second polymer extruded through the second extrudermeets at the end of the first polymer to join the first polymer to thesecond polymer, according to one embodiment;

FIG. 3D is a diagram of an example of a fourth stage of the extrusionprocess where the second polymer continues to be extruded through thesecond extruder, according to one embodiment;

FIG. 4 is a diagram of an example of an article of manufacture formedfrom the macromolecular block copolymer of the present disclosure,according to one embodiment; and

FIG. 5 is a flow diagram showing a particular embodiment of a process offorming an article of manufacture that includes a macromolecular blockcopolymer of the present disclosure.

V. DETAILED DESCRIPTION

The present disclosure describes “macromolecular” block copolymers,processes for forming macromolecular block copolymers, and articles ofmanufacture formed from the macromolecular block copolymers. As usedherein, the term “macromolecular” block copolymers is used to describe apolymeric material that includes at least two high molecular weightpolymers that are joined together at one or more locations. Themacromolecular block copolymers have different material properties at amacromolecular level, with the material properties at a particularlocation associated with a particular “block” of high molecular weightpolymer that is present at the particular location.

In contrast to “true” block copolymers that exhibit homogeneous materialproperties at the macromolecular level, the macromolecular blockcopolymers of the present disclosure may exhibit one set of materialproperties in one macromolecular region and a different set of materialproperties in another macromolecular region. As an example, in the caseof a linear article, the rigidity/flexibility along a first length ofthe linear article (corresponding to a first high molecular weightpolymer of the macromolecular block copolymer) may be greater than therigidity/flexibility along a second length of the linear article(corresponding to a second high molecular weight polymer of themacromolecular block copolymer).

As further described herein, the high molecular weight polymers that areused to form the macromolecular block copolymers of the presentdisclosure may include side-chain functional groups that may be selectedin order to facilitate chemical bonding to a particular polymer matrixmaterial. As an illustrative, non-limiting example, when the polymermatrix is EPDM rubber (ethylene propylene diene monomer rubber),norbornene side-chain functional groups may be incorporated into atleast a portion of the high molecular weight polymers in order to bondthe high molecular weight polymers into the EPDM rubber polymer matrix.In other cases, the side-chain functional groups may includenorbornenes, amines, hydroxyls, or combinations thereof (among otheralternatives) that may be selected for a particular type of polymermatrix material.

The macromolecular block copolymers of the present disclosure may beuseful in various applications where different macromolecular propertiesare desirable at different locations. As an illustrative, non-limitingexample, the macromolecular block copolymers of the present disclosuremay be used to form a reinforcement for a multi-layered rubber coolinghose of a liquid-cooled computing system in which variableflexibility/rigidity may be desirable at different locations along thelength of the rubber cooling hose. For example, a rubber cooling hosemay be used to transport a fluid (e.g., water) from one location (e.g.,a pump unit, a radiator, heat exchanger, etc.) to another location(e.g., a cold plate). In this case, it may be desirable for areinforcement for the rubber water cooling hose to be relativelyflexible at most locations and to be relatively rigid at other locations(e.g., at both ends for attachment). In this example, a macromolecularblock copolymer of the present disclosure may be used as thereinforcement, with a first high molecular weight polymer that isrelatively rigid being used at one or more locations (e.g., at the ends)and a second high molecular weight polymer that is relatively flexiblebeing used at one or more locations (e.g., along the remaining length ofthe hose).

As described further herein, the macromolecular block copolymers of thepresent disclosure may be formed using an extrusion setup that includestwo (or more) extruders (e.g., via reactive extrusion). A first highmolecular weight polymer may be extruded through a first extruder, and asecond high molecular weight polymer may be extruded through a secondextruder. Extrusion parameters (e.g., timing, temperature, etc.) may beselected such that when an end of a first segment corresponding to thefirst high molecular weight polymer is located at a joining block (alsoreferred to herein as a “joiner”), a second segment corresponding to thesecond high molecular weight polymer is extruded into the joining blockvia the second extruder to bond the second segment to the end of thefirst segment.

To illustrate, in the case of a reinforcement for a linear rubber watercooling hose (e.g., having an overall length of six feet), it may bedesirable to have a first rigid segment of a first length (e.g., onefoot) at one end, a flexible segment of a second length (e.g., threefeet), and a second rigid segment of a third length (e.g., one foot) atanother end. In this example, the first length of relatively rigid highmolecular weight polymer may be extruded using a first extruder,followed by the second length of relatively flexible high molecularweight polymer extruded using a second extruder, followed by the thirdlength of the relatively rigid high molecular weight polymer extruderusing the first extruder. As the macromolecular properties of themacromolecular block copolymer at a particular location are known basedon the extrusion parameters, the extrusion setup may be used to formnumerous segments that may be subsequently separated based on knownlocations of the individual segments.

FIG. 1 depicts an illustrative, non-limiting example of a process offorming a macromolecular block copolymer from two high molecular weightpolymers. In alternative cases, a macromolecular block copolymer may beformed from more than two high molecular weight polymers. FIG. 2 depictsan illustrative, non-limiting example of an extrusion setup thatincludes two extruders to extrude two high molecular weight polymersinto a joiner to form a macromolecular block copolymer (e.g., themacromolecular block copolymer of FIG. 1). In alternative cases, theextrusion setup may include more than two extruders to extrude more thantwo high molecular weight polymers. FIGS. 3A-3D depict various stages ofan extrusion process using the extrusion setup of FIG. 2. FIG. 4 depictsan illustrative example of an article of manufacture (e.g., areinforcement for a multi-layered rubber hose) that includes an exampleof a macromolecular block copolymer that includes two rigid blocks andone flexible block. In alternative cases, macromolecular blockcopolymers having an alternative number and/or arrangement of differenthigh molecular weight polymer segments may be incorporated into variousarticles of manufacture (e.g., living hinges, etc.). FIG. 5 depicts anexample of a process of forming an article of manufacture that includesa macromolecular block copolymer of the present disclosure.

According to an embodiment, a process of forming a macromolecular blockcopolymer is disclosed. The process includes forming a first highmolecular weight polymer using a first extruder of an extruder systemthat includes multiple extruders. The first extruded high molecularweight polymer has a first length terminating at a joiner of theextruder system and has a first set of material properties along thefirst length. The process also includes forming a second high molecularweight polymer using a second extruder of the extruder system. Thesecond extruded high molecular weight polymer has a second lengthterminating at the joiner of the extruder system and has a second set ofmaterial properties along the second length. The process furtherincludes bonding the first extruded high molecular weight polymer to thesecond extruded high molecular weight polymer to form a macromolecularblock copolymer having a first segment of the first length and a secondsegment of the second length.

According to another embodiment, a process of forming a macromolecularblock copolymer is disclosed. The process includes forming a highmolecular weight polystyrene (PS) polymer using a first extruder of anextruder system that includes multiple extruders. The extruded highmolecular weight PS polymer has a first length terminating at a joinerof the extruder system. The process also includes forming a highmolecular weight linear low density polyethylene (LLDPE) polymer using asecond extruder of the extruder system. The extruded high molecularweight LLDPE polymer has a second length terminating at the joiner. Theprocess further includes bonding the extruded high molecular weight PSpolymer to the extruded high molecular weight LLDPE polymer to form aPS-LLDPE macromolecular block copolymer. The PS-LLDPE macromolecularblock copolymer has a first segment of the first length and a secondsegment of the second length, and the first segment has a firstcharacteristic rigidity value along the first length that is greaterthan a second characteristic rigidity value of the second segment alongthe second length.

According to another embodiment, a macromolecular block copolymer isdisclosed that is formed by a process that includes forming a first highmolecular weight polymer using a first extruder of an extruder systemthat includes multiple extruders. The first extruded high molecularweight polymer has a first length terminating at a joiner of theextruder system and has a first set of material properties along thefirst length. The process also includes forming a second high molecularweight polymer using a second extruder of the extruder system. Thesecond extruded high molecular weight polymer has a second lengthterminating at the joiner of the extruder system and has a second set ofmaterial properties along the second length. The process furtherincludes bonding the first extruded high molecular weight polymer to thesecond extruded high molecular weight polymer to form a macromolecularblock copolymer having a first segment of the first length and a secondsegment of the second length.

According to an embodiment, an article of manufacture including amacromolecular block copolymer is disclosed. The macromolecular blockcopolymer includes a first extruded high molecular weight polymer and asecond extruded high molecular weight polymer bonded to the firstextruded high molecular weight polymer. The first extruded highmolecular weight polymer has a first characteristic rigidity value alonga first length, and the second extruded high molecular weight polymerhas a second characteristic rigidity value along a second length that isdifferent from the first characteristic rigidity value.

According to another embodiment, a multi-layered linear article includesa polymeric matrix material layer and a reinforcement layer bonded tothe polymeric matrix material layer. The reinforcement layer includes amacromolecular block copolymer that includes a first extruded highmolecular weight polymer, a second extruded high molecular weightpolymer bonded to the first extruded high molecular weight polymer, anda third extruded high molecular weight polymer bonded to the secondextruded high molecular weight polymer. The first extruded highmolecular weight polymer has a first characteristic rigidity value alonga first length, and the second extruded high molecular weight polymerhas a second characteristic rigidity value along a second length that isless than the first characteristic rigidity value. The third extrudedhigh molecular weight polymer has a third characteristic rigidity valuealong a third length that is different from the second characteristicrigidity value.

According to another embodiment, a reinforced hose includes a polymericmatrix material layer and a reinforcement layer bonded to the polymericmatrix material layer. The reinforcement layer includes a macromolecularblock copolymer that includes a first extruded high molecular weightpolymer, a second extruded high molecular weight polymer bonded to thefirst extruded high molecular weight polymer, and a third extruded highmolecular weight polymer bonded to the second extruded high molecularweight polymer. The first extruded high molecular weight polymer has afirst characteristic rigidity value along a first length, and the secondextruded high molecular weight polymer has a second characteristicrigidity value along a second length that is less than the firstcharacteristic rigidity value. The third extruded high molecular weightpolymer has the first characteristic rigidity value along a thirdlength.

According to an embodiment, a process of forming a macromolecular blockcopolymer includes forming a first high molecular weight polymer of afirst length. The first high molecular weight polymer includes a firstset of side-chain functional groups and has a first characteristicrigidity value along the first length. The process also includes forminga second high molecular weight polymer of a second length. The secondhigh molecular weight polymer includes a second set of side-chainfunctional groups and has a second characteristic rigidity value alongthe second length that is less than the first characteristic rigidityvalue. The process further includes bonding the second high molecularweight polymer to the first high molecular weight polymer.

According to another embodiment, a process of forming a macromolecularblock copolymer includes forming a high molecular weight polystyrene(PS) polymer of a first length. The high molecular weight PS polymerincludes a first set of side-chain functional groups and has a firstcharacteristic rigidity value along the first length. The process alsoincludes forming a high molecular weight linear low density polyethylene(LLDPE) polymer of a second length. The high molecular weight LLDPEpolymer includes a second set of side-chain functional groups and has asecond characteristic rigidity value along the second length that isless than the first characteristic rigidity value. The process furtherincludes bonding the high molecular weight LLDPE polymer to the highmolecular weight PS polymer.

According to another embodiment, a macromolecular block copolymer isdisclosed that is formed by a process that includes forming a first highmolecular weight polymer of a first length. The first high molecularweight polymer includes a first set of side-chain functional groups andhas a first characteristic rigidity value along the first length. Theprocess also includes forming a second high molecular weight polymer ofa second length. The second high molecular weight polymer includes asecond set of side-chain functional groups and has a secondcharacteristic rigidity value along the second length that is less thanthe first characteristic rigidity value. The process further includesbonding the second high molecular weight polymer to the first highmolecular weight polymer.

Referring to FIG. 1, a chemical reaction diagram 100 illustrates aparticular embodiment of a process of forming a macromolecular blockcopolymer. The first chemical reaction depicted at the top of FIG. 1illustrates an example of the synthesis of a first high molecular weightpolymer (identified as “High Molecular Weight Polymer(1)” in FIG. 1).The second chemical reaction depicted below the first chemical reactionin FIG. 1 illustrates an example of synthesis of a second high molecularpolymer (identified as “High Molecular Weight Polymer(2)” in FIG. 1).The third chemical reaction depicted below the second chemical reactionin FIG. 1 illustrates an example of the formation of a macromolecularblock copolymer by joining the first high molecular weight polymer tothe second high molecular weight polymer. As described further herein,the macromolecular block copolymer formed according to the processillustrated in FIG. 1 includes flexible segment(s) and rigid segment(s)along the length of an article. The ability to vary theflexibility/rigidity along the length of the article may be useful invarious applications that benefit from a transition of conformity (e.g.,as a reinforcement for a multi-layered rubber cooling hose for awater-cooled computing system), as illustrated and further describedherein with respect to the example of FIG. 4.

The first chemical reaction of FIG. 1 illustrates an example of aprocess of forming a rigid thermoplastic polymer that may be used toform one or more rigid segments of a macromolecular block copolymer. Inthe example of FIG. 1, the rigid thermoplastic polymer includes apolystyrene (PS) polymer that is formed by polymerizing suitablemonomers. FIG. 1 further shows that the PS polymer includes functionalside chains (designated by the letter R), where the R groups arefunctionalities that do not react during the polymerization of the firsthigh molecular weight polymer.

In FIG. 1, the integer m is used to designate a first portion of thefirst high molecular weight polymer that does not include the R groups,and the integer n is used to designate a second portion of the firsthigh molecular weight polymer that includes the R groups. The resultantpolymer depicted on the right side of the first chemical reaction inFIG. 1 is a high molecular weight polystyrene material where m and n areselected based on a degree of reaction to bond the polystyrene to aparticular polymeric matrix (not shown in FIG. 1). As described furtherherein, the functionalized starting polymers allow the polymer to bondwith the particular polymeric matrix after formation of themacromolecular block copolymer structure. As an illustrative,non-limiting example, the R groups of the first high molecular weightpolymer may be norbornene functional groups to enable chemical bondingof the high molecular weight polymer to a polymeric matrix material,such as EPDM rubber. In other cases, the side-chain functional groupsmay include norbornenes, amines, hydroxyls, or combinations thereof(among other alternatives) that may be selected for a particular type ofpolymer matrix material.

The second chemical reaction of FIG. 1 illustrates an example of aprocess of forming a flexible thermoplastic polymer that may be used toform one or more flexible segments of a macromolecular block copolymer.In the example of FIG. 1, the flexible thermoplastic polymer includes alinear low density polyethylene (LLDPE) polymer that is formed bypolymerizing suitable monomers. FIG. 1 further shows that the LLDPEpolymer includes functional side chains (designated as R′), where the R′groups are functionalities that do not react during the polymerizationof the second high molecular weight polymer.

In FIG. 1, the integer x is used to designate a first portion of thesecond high molecular weight polymer that does not include the R′groups, and the integer y is used to designate a second portion of thesecond high molecular weight polymer that includes the R′ groups. Theresultant polymer depicted on the right side of the second chemicalreaction of FIG. 1 is a high molecular weight polyethylene where x and yare selected based on degree of reaction to bond the high molecularweight polyethylene polymer to a particular polymeric matrix (not shownin FIG. 1). As an illustrative, non-limiting example, the R′ groups ofthe second high molecular weight polymer may be norbornene functionalgroups to enable chemical bonding of the high molecular weight polymerto a polymeric matrix material, such as EPDM rubber. In other cases, theside-chain functional groups may include norbornenes, amines, hydroxyls,or combinations thereof (among other alternatives) that may be selectedfor a particular type of polymer matrix material.

The third chemical reaction of FIG. 1 illustrates an example of aprocess of forming a macromolecular block copolymer from the two highmolecular weight polymers formed in the first and second chemicalreactions of FIG. 1. As illustrated and further described herein withrespect to FIG. 2 and FIGS. 3A-3D, the two high molecular weightpolymers may be joined together through a coupling/manufacturing process(e.g., reactive extrusion) in which the two polymers are free tocovalently bond at the end of the processing of the first article. Thiscreates a long chain polymer where each portion of the polymer serves asa block in the macromolecular block copolymer. In some instances, asmall block of coupling agent may be needed to join non-like polymerstogether. The resultant article then has flexible and rigid segmentsthat can be used in articles of manufacture where flexibility andrigidity is desired. Here, the resultant macromolecular block copolymerhas both rigid and flexible macromolecular block groups. Each block isof high molecular weight where each polymer would have generally beenused previously in standalone applications.

Thus, FIG. 1 illustrates an example of a process of forming amacromolecular block copolymer. The macromolecular block copolymer ofFIG. 1 may be used in various applications where flexibility isdesirable along some segment(s) and rigidity is desirable along othersegment(s). While FIG. 1 depicts an example of a PS-LLDPE macromolecularblock copolymer, in other cases, the macromolecular block copolymers ofthe present disclosure may include alternative types and/or numbers ofhigh molecular weight polymers. Further, as previously described herein,the particular type of side-chain functional groups and/or relativeportions of the high molecular weight polymers that include theside-chain functional groups may be selected based on the particularpolymeric matrix material.

FIG. 2 is a diagram 200 that illustrates an example of an extrusionsetup that includes multiple extruders to generate macromolecular blockcopolymers. In the example of FIG. 2, the extrusion setup includes afirst extruder 202 (identified as “Extruder(1)” in FIG. 2) and a secondextruder 204 (identified as “Extruder(2)” in FIG. 2). In alternativeembodiments, more than two extruders may be used. As illustrated andfurther described herein with respect to FIGS. 3A-3D, a first polymermay be extruded through the first extruder 202 into a joiner 206 to bejoined to a second polymer that is extruded through the second extruder204 into the joiner 206. While not shown in FIG. 2, the extrusionprocess may be controlled via a computing system that includes software,hardware, or a combination thereof that is configurable to extrude aparticular material in a fashion that will accurately extrude anappropriate length of material.

FIG. 2 illustrates that the first extruder 202 may be placed next to thesecond extruder 204, with each of the extruders 202, 204 utilizing itsown extrusion die. Each of the extruders 202, 204 contains a differentmaterial, and the parameters of the extruders 202, 204 are set up suchthat the polymers can be extruded through the machines. The extrusionprocess starts with one polymer being extruded to form a first segment,such as a rigid segment of a reinforcement. As that rigid section isbeing extruded, the length of the final extruded product has alreadybeen calculated to compensate for shrinkage and other dimension-changingproperties. Next, in order to transition from a rigid section to aflexible section, the second extruder 204 begins to extrude such that itis offset in order to meet at the end of the rigid section block. As thesecond extrusion passes through its die, the material is sent throughthe joiner 206 where the material from the rigid section is almostfinished passing such that the start of the flexible section is timed toallow covalent bonding between the end of the rigid section and thestart of the flexible section.

In some cases, a third extruder (not shown) may be used to covalentlybond the two polymers together via a short section of transitionpolymer. The transition polymer is selected based on the two polymersbeing joined but generally has functionalities of both polymers presentin order to induce polymerization between the two sections. Afterextruding the flexible section in a similar fashion as the rigidsection, additional rigid and/or flexible section(s) can be extrudedutilizing this process. The final article of manufacture is an extrudedmaterial that contains both rigid blocks and flexible blocks using onematerial at a time. FIGS. 3A-3D illustrate an example of multiple stagesof the aforementioned extrusion process.

FIG. 3A is a diagram 300 that illustrates an example of a first stage ofan extrusion process in which a first polymer 302 (identified as“Polymer(1)” in FIG. 3A) is extruded using the first extruder 202. In aparticular embodiment, the first polymer 302 that is extruded using thefirst extruder 202 corresponds to the first high molecular weightpolymer depicted on the right side of the first chemical reaction ofFIG. 1 (e.g., a high molecular weight polystyrene polymer).

FIG. 3B is a diagram 310 that illustrates an example of a second stageof the extrusion process in which a second polymer 312 (identified as“Polymer(2)” in FIG. 3B) is starting to extrude through the secondextruder 204 such that the end of the first polymer 302 meets the startof the second polymer 312 at the joiner 206 (as shown in FIG. 3C). In aparticular embodiment, the second polymer 312 that is extruded using thesecond extruder 204 corresponds to the second high molecular weightpolymer depicted on the right side of the second chemical reaction ofFIG. 1 (e.g., a high molecular weight LLDPE polymer).

FIG. 3C is a diagram 320 that illustrates an example of a third stage ofthe extrusion process in which the first polymer 302 is no longerextruded and only the second polymer 312 is being extruded, meeting atthe end of the first polymer 302 in the joiner 206.

While not shown in the example of FIG. 3C, in some cases, ajoining/coupling agent (e.g., a short oligomeric chain) may be used tobond the end of the first polymer 302 to the end of the second polymer312. To illustrate, in the case of a polystyrene polymer and apolyethylene polymer, the optional joining/coupling agent may beselected that includes a first functional group to bond to thepolystyrene polymer and a second functional group to bond to thepolyethylene polymer. As an illustrative, non-limiting example, thepolystyrene polymer may have oxazoline groups, the polyethylene polymermay have carboxyl groups, and a coupling reaction may join thepolystyrene polymer to the polyethylene polymer. In some cases, thejoining/coupling agent may be extruded via one or more of the extruders202, 204 (e.g., in the first extruder 202 at the end of the firstpolymer 302 and/or in the second extruder 204 at the start of the secondpolymer 312). Further, while not shown in the example of FIG. 3C, thejoiner 206 may include an additional fluid interface (e.g., a thirdextruder) to enable insertion of the optional joining/coupling agent.

FIG. 3D is a diagram 330 that illustrates an example of a fourth stageof the extrusion process in which the second polymer 312 is beingextruded.

In a particular embodiment, the first polymer 302 that is extruded viathe first extruder 202 has a first length in which relatively rigidmaterial properties are desirable for a particular application, and thesecond polymer 312 has a second length in which relatively flexiblematerial properties are desirable for the particular application. Whilenot shown in FIG. 3D, after extruding the second length of the secondpolymer 312, a third length of the first polymer 302 may be extrudedthrough the first extruder 202 to form a macromolecular block copolymerthat includes a first rigid segment, a flexible segment, and a secondrigid segment (e.g., the reinforcement illustrated in FIG. 4).

Thus, FIGS. 3A-3D illustrate an example of multiple stages of anextrusion process that may be used to form the macromolecular blockcopolymers of the present disclosure. In some cases, the extrusionprocess may be used to form additional segments of high molecular weightpolymers (such as an additional rigid segment following a flexiblesegment).

FIG. 4 is a diagram 400 that illustrates an example of a macromolecularblock copolymer reinforcement (e.g., an inner layer reinforcement for amulti-layered rubber cooling hose of a liquid-cooled computing system).In the example of FIG. 4, the reinforcement includes a first rigid block402 (identified as “Rigid Block(1)” in FIG. 4), a flexible block 404,and a second rigid block 406 (identified as “Rigid Block(2)” in FIG. 4).In other cases, the reinforcement may include an alternative numberand/or arrangement of rigid/flexible blocks.

In a particular embodiment, the first rigid block 402 corresponds to thefirst polymer 302 that is extruded via the first extruder 202 (e.g., thehigh molecular weight PS polymer of FIG. 1), and the flexible block 404corresponds to the second polymer 312 that is extruded via the secondextruder 204 (e.g., the second high molecular weight LLDPE polymer ofFIG. 1), as illustrated and further described herein with respect toFIGS. 3A-3D. In some cases, the second rigid block 406 may correspond tothe first polymer 302 (that may be extruded via the first extruder 202after extrusion of the second polymer 312, not shown in FIG. 3D).

In the example of FIG. 4, the first rigid block 402 has a first length410 (identified as “Length(1)” in FIG. 4), the flexible block 404 has asecond length 412 (identified as “Length(2)” in FIG. 4), and the secondrigid block 406 has a third length 414 (identified as “Length(3)” inFIG. 4). While FIG. 4 illustrates an example of a linear reinforcement,it will be appreciated that the processes described herein may be usedto form macromolecular block copolymers for use in formed hose designs(e.g., “S” shaped formed hose designs) with alternative numbers and/orarrangements of rigid/flexible segments that may be customized for aparticular application (e.g., for a particular liquid-cooled computingsystem design).

As an illustrative, non-limiting example, the reinforcement of FIG. 4may be used as an inner layer reinforcement for a five foot linearrubber cooling hose. In some cases, it may be desirable to have one footrigid sections on both ends of the linear rubber cooling hose. In thisexample, the first length 410 of first rigid block 402 is one foot, thesecond length 412 is three feet, and the third length 414 is one foot.The rigid blocks 402, 404 may improve the ability to couple between thehose and a termination, such as a barb/clamp, resulting in improved sealsecurity due to improved grip around the termination. As shown at thebottom of FIG. 4, the flexible block 404 may enable bending (e.g.,around corners in a liquid-cooled computing system).

In a particular embodiment, a reinforcement having a similar design tothe reinforcement illustrated in FIG. 4 may be used to reinforce alinear hose, and the reinforced linear hose may satisfy particular bendradius criteria. As an example, for a one-quarter inch hose, the bendradius criteria may be a bend radius of at least 0.75 inches (withoutkinking). As another example, for a one-half inch hose, the bend radiuscriteria may be a bend radius of at least 2.5 inches (without kinking).As a further example, for a one inch hose, the bend radius criteria maybe a bend radius of at least 6 inches (without kinking).

Cord-reinforced rubber structures, such as cord-reinforced rubber hoses,provide strength and durability for water cooling systems whereasnon-reinforced hoses tend to sag and eventually kink over time.Typically, cord reinforcement includes steel cord that limits theflexibility of the hoses. Thermoplastics represent a suitablereplacement but are generally lacking due to a single set of materialproperties (e.g., flexibility or rigidity) existing along the length ofthe hose or article. The reinforcement material illustrated in FIG. 4 isan example of a cord replacement that enables the hose to have rigidends while also having a flexible middle section for improved bendingand shaping (as shown at the bottom of FIG. 4).

In manufacturing of a thermoplastic corded rubber hose using themacromolecular block copolymers of the present disclosure, a first hoselayer may be extruded onto a mandrel and partially cured. Next, the cordreplacement may be wrapped around the hose. Next, the outer covermaterial may be extruded over the top of the hose, and the whole hoseassembly may be cured using standard curing conditions. During curing,the functionalities on the side chains of the macromolecular blockcopolymer reinforcement react with the rubber to form covalent bonds,reducing or eliminating delamination. The hose may then be cured todesired dimensions such that cuts are made in the rigid regions and notthe flexible regions. This also allows for better termination of thehose while providing the desired flexibility.

Thus, FIG. 4 illustrates an example of an article of manufacture (e.g.,a reinforcement for a multi-layered rubber cooling hose) formed from themacromolecular block copolymers of the present disclosure. The abilityto vary the material properties (e.g., flexibility/rigidity) along thelength of the article enables improved bending and shaping, which may beuseful in some liquid-cooled computing systems (among other possiblealternative uses).

Referring to FIG. 5, a flow diagram illustrates an example of a process500 of forming an article of manufacture that includes a macromolecularblock copolymer of the present disclosure. In a particular embodiment,the macromolecular block copolymer may correspond to the examplePS-LLDPE macromolecular block copolymer of FIG. 1. In a particularembodiment, the macromolecular block copolymer may be formed using theextrusion setup depicted in FIG. 2, according to the example extrusionprocess depicted in FIGS. 3A-3D. In a particular embodiment, themacromolecular block copolymer may be used as a reinforcement (e.g., fora multi-layered rubber water-cooling hose of a water-cooled computingsystem) that includes flexible and rigid sections, such as themacromolecular block copolymer reinforcement depicted in the example ofFIG. 4.

The process 500 includes forming a first high molecular weight polymerusing a first extruder of an extruder system that includes multipleextruders, at 502. The first extruded high molecular weight polymer hasa first length terminating at a joiner of the extruder system. Forexample, the extruder system may correspond to the extruder setupdepicted in FIG. 2 that includes the first extruder 202, the secondextruder 204, and the joiner 206. As shown in the example of FIGS.3A-3C, the first extruder 202 may be used to form the first polymer 302terminating at the joiner 206. In some cases, the first polymer 302 maycorrespond to the first high molecular weight PS polymer depicted inFIG. 1. In a particular embodiment, the first polymer 302 extruded usingthe first extruder 202 may correspond to the first rigid block 402 ofFIG. 4 that has the first length 410.

The process 500 includes forming a second high molecular weight polymerusing a second extruder of the extruder system, at 504. The secondextruded high molecular weight polymer has a second length terminatingat the joiner of the extruder system. For example, as shown in theexample of FIGS. 3B and 3C, the second extruder 204 may be used to formthe second polymer 312 terminating at the joiner 206. In some cases, thesecond polymer 312 may correspond to the second high molecular weightLLDPE polymer depicted in FIG. 1. In a particular embodiment, the secondpolymer 312 extruded using the second extruder 204 may correspond to theflexible block 404 of FIG. 4 that has the second length 412.

The process 500 includes bonding the first extruded high molecularweight polymer to the second high molecular weight polymer at the joinerto form a macromolecular block copolymer, at 506. The macromolecularblock copolymer has a first segment of the first length and a secondsegment of the second length. For example, referring to FIG. 3C, thefirst polymer 302 may be bonded to the second polymer 312 at the joiner206.

In the particular embodiment illustrated in FIG. 5, the process 500 alsoincludes forming a third high molecular weight polymer using one of theextruders of the extruder system, at 508. The third extruded highmolecular weight polymer has a third length terminating at the joiner.For example, while not shown in FIG. 3D, after extruding the secondpolymer 312, the first extruder 202 (or another extruder, in cases ofextruder systems with more than two extruders) may be used to form athird segment of the first polymer 302 terminating at the joiner 206. Insome cases, the first polymer 302 may correspond to the first highmolecular weight PS polymer depicted in FIG. 1.

In the particular embodiment illustrated in FIG. 5, the process 500further includes bonding the third high molecular weight polymer to thesecond high molecular weight polymer to form a third segment of themacromolecular block copolymer, at 510. In a particular embodiment, thethird segment of the first polymer 302 extruded using the first extruder202 may correspond to the second rigid block 406 of FIG. 4 that has thethird length 414.

Thus, FIG. 5 illustrates an example of a process of forming an articleof manufacture that includes a macromolecular block copolymer. In theparticular embodiment illustrated in FIG. 5, the macromolecular blockcopolymer includes a first segment (e.g., a rigid segment), a secondsegment (e.g., a flexible segment), and a third segment (e.g., a secondrigid segment). In other cases, the macromolecular block copolymer mayinclude an alternative number of segments, an alternative arrangement ofsegments, alternative numbers of high molecular weight polymers, or acombination thereof.

The previous description of the disclosed embodiments is provided toenable any person skilled in the art to make or use the disclosedembodiments. Various modifications to these embodiments will be readilyapparent to those skilled in the art, and the generic principles definedherein may be applied to other embodiments without departing from thescope of the disclosure. Thus, the present disclosure is not intended tobe limited to the embodiments shown herein but is to be accorded thewidest scope possible consistent with the principles and features asdefined by the following claims.

The invention claimed is:
 1. An article of manufacture, comprising: ablock copolymer comprising: a first extruded polymer having a firstcharacteristic rigidity along a first length; and at least a portion ofa second extruded polymer bonded to at least a portion of the firstextruded polymer, the second extruded polymer having a secondcharacteristic rigidity along a second length that is different from thefirst characteristic rigidity, wherein at least one of the firstextruded polymer or the second extruded polymer includes side-chainfunctional groups for chemically bonding the block copolymer to apolymeric matrix material.
 2. The article of manufacture of claim 1,wherein the polymeric matrix material includes ethylene propylene dienemonomer (EPDM) rubber.
 3. The article of manufacture of claim 1, whereinthe side-chain functional groups include amine groups, norbornenegroups, hydroxyl groups, or a combination thereof.
 4. The article ofmanufacture of claim 1, wherein the block copolymer further comprises atleast a portion of a third extruded polymer bonded to at least a portionof the second extruded polymer, the third extruded polymer having athird characteristic rigidity along a third length that is differentfrom the second characteristic rigidity.
 5. The article of manufactureof claim 4, wherein the third characteristic rigidity corresponds to thefirst characteristic rigidity.
 6. The article of manufacture of claim 1,wherein the first extruded polymer includes a polystyrene (PS) polymer,and wherein the second extruded polymer includes a linear low densitypolyethylene (LLDPE) polymer.
 7. The article of manufacture of claim 6,wherein the PS polymer has an oxazoline group.
 8. The article ofmanufacture of claim 6, wherein the LLDPE polymer has a carboxyl group.9. An article of manufacture, comprising: a block copolymer comprising:a first extruded polymer having a first characteristic rigidity along afirst length, wherein the first extruded polymer includes a polystyrene(PS) polymer; and at least a portion of a second extruded polymer bondedto at least a portion of the first extruded polymer, the second extrudedpolymer having a second characteristic rigidity along a second lengththat is different from the first characteristic rigidity, wherein thesecond extruded polymer includes a linear low density polyethylene(LLDPE) polymer, and wherein at least one of the PS polymer or the LLDPEpolymer includes side-chain functional groups for chemically bonding theblock copolymer to a polymeric matrix material.
 10. The article ofmanufacture of claim 9, wherein the polymeric matrix material includesethylene propylene diene monomer (EPDM) rubber.
 11. The article ofmanufacture of claim 9, wherein the side-chain functional groups includeamine groups, norbornene groups, hydroxyl groups, or a combinationthereof.
 12. The article of manufacture of claim 9, wherein the PSpolymer has an oxazoline group.
 13. The article of manufacture of claim9, wherein the LLDPE polymer has a carboxyl group.
 14. The article ofmanufacture of claim 9, wherein the block copolymer further comprises atleast a portion of a third extruded polymer bonded to at least a portionof the second extruded polymer, the third extruded polymer having athird characteristic rigidity along a third length that is differentfrom the second characteristic rigidity.
 15. The article of manufactureof claim 14, wherein the third characteristic rigidity corresponds tothe first characteristic rigidity.
 16. An article of manufacture,comprising: a block copolymer comprising: a first extruded polymerhaving a first characteristic rigidity along a first length, wherein thefirst extruded polymer includes a polystyrene (PS) polymer; at least aportion of a second extruded polymer bonded to at least a portion of thefirst extruded polymer, the second extruded polymer having a secondcharacteristic rigidity along a second length that is different from thefirst characteristic rigidity, wherein the second extruded polymerincludes a linear low density polyethylene (LLDPE) polymer, and whereinat least one of the PS polymer or the LLDPE polymer includes side-chainfunctional groups for chemically bonding the block copolymer to apolymeric matrix material; and a third extruded polymer bonded to thesecond extruded polymer, the third extruded polymer having a thirdcharacteristic rigidity along a third length that is different from thesecond characteristic rigidity.
 17. The article of manufacture of claim16, wherein the third characteristic rigidity corresponds to the firstcharacteristic rigidity.
 18. The article of manufacture of claim 16,wherein the polymeric matrix material includes ethylene propylene dienemonomer (EPDM) rubber.
 19. The article of manufacture of claim 16,wherein the PS polymer has an oxazoline group and the LLDPE polymer hasa carboxyl group.